CN113121782B - Polyurethane elastomer raw material, polyurethane elastomer and preparation method thereof - Google Patents
Polyurethane elastomer raw material, polyurethane elastomer and preparation method thereof Download PDFInfo
- Publication number
- CN113121782B CN113121782B CN201911396675.1A CN201911396675A CN113121782B CN 113121782 B CN113121782 B CN 113121782B CN 201911396675 A CN201911396675 A CN 201911396675A CN 113121782 B CN113121782 B CN 113121782B
- Authority
- CN
- China
- Prior art keywords
- polyurethane elastomer
- compound
- membered saturated
- substituted
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002994 raw material Substances 0.000 title abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 22
- 125000004452 carbocyclyl group Chemical group 0.000 claims description 21
- 229940126062 Compound A Drugs 0.000 claims description 19
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 19
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- -1 hydroxyl hydrogen Chemical compound 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 10
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- 230000008439 repair process Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
Abstract
The invention discloses a polyurethane elastomer raw material, a polyurethane elastomer and a preparation method thereof. The structure of the polyurethane elastomer is shown as a formula I. The polyurethane elastomer has ultrahigh strength and toughness, excellent thermal stability and tear resistance, and good application and popularization prospects.
Description
Technical Field
The invention relates to a polyurethane elastomer raw material, a polyurethane elastomer and a preparation method thereof.
Background
In recent years, self-repairing polyurethane materials based on reversible covalent bonds have been well developed, but most of various self-repairing polyurethane materials have poor mechanical properties (such as strength and toughness) and greatly limit the application of the self-repairing polyurethane materials. Chinese patent application CN107236106A utilizes the reaction of an aromatic hydroxyl-terminated chain extender containing acylhydrazone bond and an isocyanate-terminated polyurethane prepolymer to prepare the self-repairing polyurethane, and the tensile strength of the self-repairing polyurethane material is maximally improved to 2.75MPa, and the elongation at break is maximally improved to 495.37%. However, the method can not meet the application occasions with high requirements on the mechanical properties of the self-repairing polyurethane, and the mechanical properties of the self-repairing polyurethane still have a large improvement space.
Disclosure of Invention
The invention aims to overcome the defect of poor mechanical properties such as strength, toughness and the like of a self-repairing polyurethane material in the prior art, and provides a polyurethane elastomer raw material, a polyurethane elastomer and a preparation method thereof. The polyurethane elastomer has ultrahigh strength and toughness, and has excellent thermal stability and tear resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a polyurethane elastomer has a structure shown in a formula I:
wherein R is a Is thatWherein, the ring Q is 3-10 membered saturated carbocyclyl or R substituted 3-10 membered saturated carbocyclyl; r is R a1 Is connected with 1-bit N, R a3 Is connected with the 2-bit N; r is R a1 、R a2 And R is a3 Each independently is a bond, - (CH) 2 ) 1～4 -, 3-to 10-membered saturated carbocyclyl, R-substituted 3-to 10-membered saturated carbocyclyl, 6-to 18-membered aryl or R-substituted 6-to 18-membered aryl; and R is a1 、R a2 And R is a3 At most one of which is a 6-18 membered aryl or R-substituted 6-18 membered aryl;
alternatively, R a Is- (CH) 2 ) 2～10 -or R-substituted- (CH) 2 ) 2～10 -；
The R is one or more, and each R is independently C 1-4 Alkyl or halo C 1-4 An alkyl group;
R b removing residual structures of hydroxyl hydrogen at two ends of polyether glycol or polyester glycol;
R c is- [ (CH) 2 ) i -(NHC(＝O)) j -(CH 2 ) k ] x -wherein i, j, k and x are each independently 0, 1 or 2; when i, j and k are simultaneously 0, and/or x is 0, R c Is a connecting key;
m＝20～40；
the molecular weight distribution index of the polyurethane elastomer is 1-2.5.
In the present invention, the ring Q is preferably a 5-to 8-membered saturated carbocyclyl group or an R-substituted 5-to 8-membered saturated carbocyclyl group; the ring Q is more preferably a 6-membered saturated carbocyclyl or an R-substituted 6-membered saturated carbocyclyl; the R-substituted 6-membered saturated carbocyclyl is preferably C 1-4 Alkyl substituted 6 membered saturated carbocyclyl, more preferably methyl substituted 6 membered saturated carbocyclyl.
In the present inventionPreferably, the R a1 、R a2 And R is a3 Respectively are a connecting bond, -CH 2 -and a connection key. Preferably, said R a1 、R a2 And R is a3 Respectively are a connecting bond, -CH 2 -and 6-membered saturated carbocyclyl. Preferably, said R a1 、R a2 And R is a3 Respectively are a connecting bond, -CH 2 -and phenyl.
In the present invention, R a Preferably- (CH) 2 ) 6～8 -or R-substituted- (CH) 2 ) 6～8 -, more preferably- (CH) 2 ) 6 -。
In the present invention, R is more preferably a Is that
More preferably
In the present invention, preferably, the polyether glycol or polyester glycol is selected from polytetrahydrofuran glycol, polyethylene adipate glycol, polyethylene glycol adipate, 1, 4-butanediol adipate glycol and polyethylene glycol. The polyether glycol or polyester glycol preferably has a number average molecular weight of 2000 to 3000.
In the present invention, R is more preferably b Is thatn＝28～42。
In the present invention, preferably, R c Is a bond, - (CH) 2 ) 4 -or-CH 2 -NHC(＝O)-CH 2 -。
In a preferred embodiment of the present invention, the polyurethane elastomer has the structural formula shown in formula I-1:
wherein m is 38 and n is 28; the polyurethane elastomer has a molecular weight distribution index (PDI) of 1.66.
In a preferred embodiment of the present invention, the polyurethane elastomer has the structural formula shown in formula I-2:
wherein m is 35, n is 28; the polyurethane elastomer has a molecular weight distribution index (PDI) of 1.86.
In a preferred embodiment of the present invention, the polyurethane elastomer has the structural formula shown in formula I-3:
wherein m is 28 and n is 28; the molecular weight distribution index (PDI) of the polyurethane elastomer was 2.23.
In a preferred embodiment of the present invention, the polyurethane elastomer has the structural formula shown in formula I-4:
wherein m is 22 and n is 28; the polyurethane elastomer has a molecular weight distribution index (PDI) of 1.96.
The invention also provides a preparation method of the polyurethane elastomer, which comprises the following steps:
(1) In a solvent, under the protection of gas, under the temperature of 60-80 ℃, under the action of a catalyst, carrying out a prepolymerization reaction on the compound A and the compound B to obtain a prepolymer;
(2) In a solvent, under the protection of gas, carrying out polymerization reaction on the prepolymer obtained in the step (1) and a compound C at the temperature of 30-50 ℃ to obtain a polyurethane elastomer shown in a formula I;
wherein R is a 、R b And R is c And m are as defined above; the mol ratio of the compound A to the compound B to the compound C is 2 (0.9-1.1) and 0.9-1.1.
In the present invention, the molar ratio of the compound A, the compound B and the compound C is preferably 2:1:1.
In a preferred embodiment of the present invention, the compound A is(isophorone diisocyanate), said compound B is +>(polytetrahydrofuran, n=28), said compound C is +.>(adipic acid dihydrazide).
In a preferred embodiment of the present invention, the compound A is(dicyclohexylmethane diisocyanate), said compound B being +.>(polytetrahydrofuran, n=28), said compound C is +.>(adipic acid dihydrazide).
In a preferred embodiment of the present invention, the compound A is(Isofluorenone di)Isocyanate), said compound B being +.>(polytetrahydrofuran, n=28), said compound C is +.>(oxalic acid dihydrazide).
In a preferred embodiment of the present invention, the compound A is(hexamethylene diisocyanate), said compound B being +.>(polytetrahydrofuran, n=28), said compound C is +.>(adipic acid dihydrazide).
In the present invention, the solvent in step (1) or step (2) may be a solvent conventionally used in the art, preferably a polar organic solvent such as one or more of N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide (DMAc) and dimethylsulfoxide. The solvent is preferably N, N-dimethylacetamide (DMAc). The solvents described in step (1) or step (2) are the same or different.
In the present invention, in step (1) or step (2), the gas is preferably nitrogen.
In step (1) of the present invention, the catalyst may be an organotin catalyst or a tertiary amine catalyst conventional in such reactions in the art, preferably dibutyltin dilaurate (DBTDL), stannous octoate, triethylenediamine, bis (dimethylaminoethyl) ether or N, N-dimethylcyclohexylamine. The catalyst may be used in an amount conventional for such reactions, the mass ratio of the catalyst to the compound A being preferably 1: (100-500). For example, when the compound A is isophorone diisocyanate and the catalyst is dibutyltin dilaurate, the mass ratio of the two is preferably 1:111.
In the present invention, in the step (1), the time of the prepolymerization may be 2 to 5 hours, preferably 3 hours.
In the present invention, in the step (1), the temperature of the prepolymerization is preferably 70 ℃.
In the present invention, the compound B is preferably subjected to a water removal treatment prior to the step (1). The water removal treatment may be carried out by a method conventional in the art, preferably by stirring the compound B at 110℃under vacuum for 1 hour.
In the present invention, in the step (2), the temperature of the polymerization reaction is preferably 40 ℃.
In the present invention, in the step (2), the polymerization time may be 10 to 20 hours, preferably 15 hours.
In the present invention, step (2) is preferably: after the prepolymerization reaction in the step (1) is finished, the temperature of the system is cooled to 30-50 ℃, and a solution of the compound C is directly added into the system to carry out polymerization reaction.
In the present invention, it is preferable to carry out the post-treatment after the polymerization reaction in the step (2) is completed. The post-treatment may be carried out by a method conventional in the art, and preferably, the reaction solution after completion of the polymerization reaction is heated to volatilize the solvent, followed by vacuum drying. The temperature of the heating may be conventionally selected according to the nature of the solvent, preferably 80 ℃. The heating time can be determined according to the solvent volatilization condition, and is preferably 12h. The temperature of the drying may be conventionally selected according to the nature of the solvent, and is preferably 80 ℃. The drying time can be determined according to the actual drying condition, and is preferably 24 hours.
The invention also provides a polyurethane elastomer, which is prepared by the preparation method.
The invention provides a polyurethane elastomer raw material, which comprises a compound A, a compound B and a compound C, wherein,
the compound A is OCN-R a -NCO，
The compound B is HO-R b -OH，
The compound C is
Wherein R is a 、R b And R is c Is as defined above; the molar ratio of the compound A to the compound B to the compound C is 2 (0.9-1.1): (0.9-1.1), preferably 2:1:1.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the invention provides a polyurethane elastomer shown in a formula I, which has the advantages of ultrahigh strength and toughness (the tensile strength is more than 60MPa, even up to 80MPa, the elongation at break is more than 1400%, even up to 1706%), excellent tear resistance and thermal stability, and good application and popularization prospects.
Drawings
FIGS. 1 to 6 are the tensile curves of polyurethane elastomer samples of examples 1 to 4 and comparative examples 1 to 2, respectively, according to the present invention.
FIG. 7 is a graph showing the cyclic stretching curves of polyurethane elastomer samples of example 1 of the present invention at various waiting times.
FIG. 8 is a graph of hysteresis area and residual strain for various wait times for polyurethane elastomer samples of example 1 of the present invention.
FIG. 9 is a plot of the tensile curve of the polyurethane elastomer samples of example 1 of the present invention with and without notches.
FIG. 10 is a tensile curve of a polyurethane elastomer sample of example 1 of the present invention repaired at 100℃for various times.
FIG. 11 is a plot showing the tensile curve of a polyurethane elastomer sample of example 1 of the present invention repaired for 36h at various temperatures.
FIG. 12 is a plot of storage modulus versus loss modulus as a function of temperature for polyurethane elastomer samples of example 1 of the present invention.
FIG. 13 is a graph showing the change in loss tangent with temperature of a polyurethane elastomer sample of example 1 of the present invention.
FIG. 14 is a thermal weight loss curve of a polyurethane elastomer sample of example 1 of the present invention.
Fig. 15 is a wide angle X-ray diffraction pattern of a polyurethane elastomer sample of example 1 of the present invention.
FIG. 16 is a small angle X-ray diffraction pattern of a polyurethane elastomer sample of example 1 of the present invention.
FIG. 17 is an ultraviolet spectrum of a polyurethane elastomer sample of example 1 of the present invention.
FIGS. 18 to 23 are nuclear magnetic patterns of polyurethane elastomer samples of examples 1 to 4 and comparative examples 1 to 2, respectively, according to the present invention.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
(1) Adding 10g of polytetrahydrofuran (PTMEG, mn=2000, n=28) into a three-port bottle provided with a stirrer and a vacuum pumping device, adjusting the temperature value to 110 ℃, stirring and vacuumizing for 1h under vacuum, reducing the temperature to 70 ℃ after vacuumizing is finished, dissolving 2.22g of isophorone diisocyanate (IP) and 0.02g of dibutyltin dilaurate (DBTDL) into 5ml of N, N-dimethylacetamide (DMAc), adding into the three-port bottle, reacting for 3h under the protection of nitrogen, and finally reducing the temperature to 40 ℃;
(2) Dissolving 0.86g of adipic Acid Dihydrazide (AD) into 50mL of N, N-dimethylacetamide at 100 ℃, rapidly adding the dissolved adipic acid dihydrazide solution into a three-necked flask by using a syringe, and reacting for 15h under the protection of nitrogen;
(3) Pouring the reaction solution into a glass culture dish, heating at 80 ℃ for 12 hours to volatilize the solvent, then placing the culture dish with the sample into a vacuum oven at 80 ℃, and vacuum drying for 24 hours to obtain the polyurethane elastomer, wherein the structure of the polyurethane elastomer is shown as a formula I-1.
Example 2
(1) Adding 10g of polytetrahydrofuran (PTMEG, mn=2000) into a three-port bottle provided with a stirrer and a vacuum pumping device, adjusting the temperature value to 110 ℃, stirring and vacuumizing for 1h under vacuum conditions, reducing the temperature to 70 ℃ after vacuumizing is finished, dissolving 2.62g of dicyclohexylmethane diisocyanate and 0.02g of dibutyltin dilaurate (DBTDL) into 5mL of N, N-dimethylacetamide (DMAc), adding into the three-port bottle, reacting for 3h under the protection of nitrogen, and finally reducing the temperature to 40 ℃;
(2) Dissolving 0.86g of adipic Acid Dihydrazide (AD) into 50mL of N, N-dimethylacetamide at 100 ℃, rapidly adding the dissolved adipic acid dihydrazide solution into a three-necked flask by using a syringe, and reacting for 15h under the protection of nitrogen;
(3) Pouring the reaction solution into a glass culture dish, heating at 80 ℃ for 12 hours to volatilize the solvent, then placing the culture dish with the sample into a vacuum oven at 80 ℃, and vacuum drying for 24 hours to obtain the polyurethane elastomer, wherein the structure of the polyurethane elastomer is shown as a formula I-2.
Example 3
(1) Adding 10g of polytetrahydrofuran (PTMEG, mn=2000) into a three-necked flask equipped with a stirrer and a vacuum pumping device, adjusting the temperature value to 110 ℃, stirring and vacuumizing for 1h under vacuum, after vacuumizing, reducing the temperature to 70 ℃, dissolving 2.22g of isophorone diisocyanate (IP) and 0.02g of dibutyltin dilaurate (DBTDL) into 5mL of N, N-dimethylacetamide (DMAc), adding into the three-necked flask, reacting for 3h under the protection of nitrogen, and finally reducing the temperature to 40 ℃;
(2) Dissolving 0.59g of oxalic acid dihydrazide in 70mL of N, N-dimethylacetamide at 130 ℃, rapidly adding the dissolved adipic acid dihydrazide solution into a three-mouth bottle by using a syringe, and reacting for 15h under the protection of nitrogen;
(3) Pouring the reaction solution into a glass culture dish, heating at 80 ℃ for 12 hours to volatilize the solvent, then placing the culture dish with the sample into a vacuum oven at 80 ℃, and vacuum drying for 24 hours to obtain the polyurethane elastomer, wherein the structure of the polyurethane elastomer is shown as a formula I-3.
Example 4
The procedure and conditions were the same as in example 1 except that 1.68g of hexamethylene diisocyanate was used in place of 2.22g of isophorone diisocyanate (IP) in example 1, and the structure of the resulting polyurethane elastomer was shown in formula I-4.
Comparative example 1
The procedure and conditions were otherwise identical to example 1 except that 1.74g of toluene 2, 4-diisocyanate (TDI) was used in place of 2.22g of isophorone diisocyanate (IP) in example 1, and the resulting polyurethane elastomer had the structure shown in formula II.
Comparative example 2
The procedure and conditions were the same as in example 1 except that 0.3g of ethylenediamine was used instead of 0.86g of Adipic Dihydrazide (AD) in example 1, and the structure of the resulting polyurethane elastomer was shown in formula III.
Effect example 1: structural characterization
1. Nuclear magnetic characterization
The polyurethane elastomers prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to nuclear magnetic characterization, specifically, 10mg of the sample was dissolved in 0.5mL of anhydrous deuterated chloroform on a Bruker 500M nuclear magnetic resonanceProceed H 1 The results of the test are shown in FIGS. 18 to 23.
2. Molecular weight and molecular weight distribution index (PDI)
The polyurethane elastomers obtained in examples 1 to 4 and comparative examples 1 to 2 were measured by using a Waters 2410 Gel Permeation Chromatography (GPC) method, and the sample concentration was about 2 to 3mg/mL, and the sample loading amount was 60 μl, using tetrahydrofuran as a mobile phase, measured at a flow rate of 1 mL/min. The polymerization degree m (calculated from the number average molecular weight measured) and PDI of each sample are shown in Table 1.
TABLE 1
| Sample of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| m | 38 | 35 | 28 | 22 | 11 | 18 |
| n | 28 | 28 | 28 | 28 | 28 | 28 |
| PDI | 1.66 | 1.86 | 2.23 | 1.96 | 1.85 | 2.53 |
Effect example 2: infrared test
The polyurethane elastomers prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to infrared test.
The testing method comprises the following steps: 7mg of the sample was dissolved in tetrahydrofuran and film was formed on a silicon wafer for testing.
Test instrument: infrared spectrometer VERTEX 80V (Brucker)
Infrared carbonyl removal of samples (1800-1600 cm) on Origin 7.5 -1 ) The peaks were separated, and the degree of hydrogen bonding was calculated from the assignment of the groups represented by each peak and the area ratio, and the results are shown in table 2. It can be seen that the degree of hydrogen bonding of the polyurethane elastomers of examples 1 to 4 of the present invention is 50% or more, even as high as 79.8%, far higher than that of the comparative example.
TABLE 2
Effect example 2: mechanical property test
1. Tensile test
The polyurethane elastomers prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to a tensile TEST at a tensile rate of 50mm/min in a 410R250 tensiometer (TEST RESOURCES inc., USA) at an effective area of 12mm×20mm×0.8mm, at room temperature, and at least 5 parallel samples were taken for each sample, and an average was taken. The tensile curves of the samples are shown in FIGS. 1 to 6, and the tensile strength and elongation at break are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the polyurethane elastomers of examples 1 to 4 all had tensile strengths of 60MPa or more and elongation at break of 1400% or more, while having higher strengths and toughness. Comparative examples 1 and 2 have a low tensile strength although the elongation at break is high.
2. Rebound resilience test
The dumbbell-shaped sample (effective area 12mm×20mm×0.8 mm) of the polyurethane elastomer prepared in example 1 was prepared, and according to the method of the tensile test described above, the sample was first loaded to 400%, then unloaded, and the same loading and unloading were repeated for different times (1 min, 5min, 15min, 30min, 60min, 120min and 180 min), and the cyclic stretching curves of the sample were obtained as shown in fig. 7, and the hysteresis areas and residual strain curves corresponding to different waiting times were as shown in fig. 8. It can be seen that the sample has good rebound resilience, and when the sample is stretched for 400%, the hysteresis area of the sample is recovered to 93% of that of the original sample, and the residual strain is recovered to 12%.
3. Fracture energy test
The polyurethane elastomer prepared in example 1 was prepared into two rectangular samples (16 mm. Times.5 mm. Times.0.6 mm), and a 1mm notch was cut in the middle of one sample with a scalpel, and the other sample was not treated. The sample was clamped in the tensiometer, the distance between the upper and lower clamping plates was 10mm, the stretching speed was 3mm/min, the test temperature was room temperature, and a stretching curve was obtained by performing a stretching test, as shown in fig. 9. The breaking energy G is calculated according to the following formula c ＝221.4KJ/m 2 It can be seen that the sample has very good tear resistance.
Wherein c represents the length of the notch, lambda c Represents the fracture strain of the unnotched sample, w represents the strain-strain curve obtained by integrating the stress curve of the unnotched sample up to lambda c The calculated strain energy.
Effect example 3: repair Performance test
The polyurethane elastomer prepared in example 1 was prepared into a rectangular sample (40 mm. Times.20 mm. Times.0.8 mm), and a incision was made in the middle with a scalpel, and the sample was put into an oven at a certain temperature for repair; the repaired sample was cut into a dumbbell shape (effective area 12 mm. Times.2 mm. Times.0.8 mm) with the incision in the middle, and a tensile curve was obtained in accordance with the method of the tensile test in effect example 2. FIG. 10 shows the tensile curves of samples repaired at 100deg.C for different times (original, 6h, 12h, 24h and 36 h) and FIG. 11 shows the tensile curves of samples repaired at different temperatures (original, 70 ℃, 80 ℃, 90 ℃ and 100 ℃) for 36 h. Stress and strain repair efficiencies of samples at 100 ℃ for different times and at different temperatures for 36h are shown in table 4.
TABLE 4 Table 4
It can be seen that the repair efficiency of the sample was gradually increased with the increase of the repair time when the repair temperature of the sample was 100 c, and the mechanical properties of the sample were almost completely recovered when the sample was repaired for 36 hours. When the sample is repaired for 36h at different temperatures, the repair efficiency is gradually improved along with the increase of the repair temperature.
Effect example 4: thermal performance testing
1. Dynamic mechanical thermal analysis (DMA)
The polyurethane elastomer prepared in example 1 was prepared into rectangular samples (50 mm. Times.5 mm. Times.0.6 mm) and tested on an instrument TAQ800 at a temperature ranging from-100℃to 150℃and a heating rate of 5℃per minute. Fig. 12 is a plot of storage modulus versus loss modulus for a sample as a function of temperature, and it can be seen that both storage modulus and loss modulus decrease as the temperature of the sample increases. FIG. 13 shows the change in loss tangent with temperature for a sample having a soft segment Tg of-66℃and a hard segment Tg of 77 ℃.
2. Thermogravimetric analysis test
10g of the polyurethane elastomer prepared in example 1 was subjected to thermogravimetric analysis on a TAQ500 at a test temperature ranging from 25 to 800℃and a heating rate of 10℃per minute, and tested under an air atmosphere. FIG. 14 is a graph of thermal weight loss of a sample, showing that the sample has high thermal stability and an initial decomposition temperature of 250℃or higher.
Effect example 5: microstructure characterization
1. Wide angle X-ray diffraction (XRD)
The polyurethane elastomer prepared in example 1 was prepared into a rectangular sample (20 mm. Times.20 mm. Times.0.8 mm) and tested on a D/MAX2550 instrument, and the results are shown in FIG. 15. As can be seen from fig. 15, the sample was amorphous without crystallization.
2. Small angle X-ray diffraction (SAXS)
The polyurethane elastomer prepared in example 1 was prepared into rectangular samples (10 mm. Times.5 mm. Times.0.5 mm) and tested on a SAXSess mc2 instrument, the results of which are shown in FIG. 16. As can be seen from fig. 16, a strong scattering peak was observed at q=0.68 nm, demonstrating that microphase separation of the sample occurred.
Effect example 6: ultraviolet testing
A sample of the polyurethane elastomer prepared in example 1, 0.6mm, was subjected to UV testing using a UV spectrophotometer UV-2700 (SHIMADZU) according to conventional methods in the art, and the results are shown in FIG. 17. The sample has a light transmittance of 90% at 550nm and exhibits good transparency.
Claims (15)
1. A polyurethane elastomer is characterized in that the structure is shown as a formula I:
wherein,
R a is thatWherein, the ring Q is 5-8 membered saturated carbocyclyl or R substituted 5-8 membered saturated carbocyclyl; r is R a1 Is connected with 1-bit N, R a3 Is connected with the 2-bit N;
the R is a1 、R a2 And R is a3 Respectively are a connecting bond, -CH 2 -and a connecting key; alternatively, the R a1 、R a2 And R is a3 Respectively are a connecting bond, -CH 2 -and 6 membered saturated carbocyclyl;
alternatively, R a Is- (CH) 2 ) 2～10 -or R-substituted- (CH) 2 ) 2～10 -；
The R is one or more, and each R is independently C 1-4 Alkyl or halo C 1-4 An alkyl group;
R b removing residual structures of hydroxyl hydrogen at two ends of polyether glycol or polyester glycol; the number average molecular weight of the polyether glycol or the polyester glycol is 2000-3000;
R c is- [ (CH) 2 ) i -(NHC(＝O)) j -(CH 2 ) k ] x -wherein j = 0, i, k and x are each independently 1 or 2;
m＝20～40；
the molecular weight distribution index of the polyurethane elastomer is 1-2.5.
2. The polyurethane elastomer of claim 1, wherein the ring Q is a 6 membered saturated carbocyclyl or an R-substituted 6 membered saturated carbocyclyl.
3. The polyurethane elastomer of claim 2, wherein the R-substituted 6-membered saturated carbocyclyl is C 1-4 Alkyl substituted 6 membered saturated carbocyclyl.
4. The polyurethane elastomer of claim 2, wherein the R-substituted 6-membered saturated carbocyclyl is a methyl-substituted 6-membered saturated carbocyclyl.
5. The polyurethane elastomer of claim 1, wherein R a Is- (CH) 2 ) 6～8 -or R-substituted- (CH) 2 ) 6～8 -；
Alternatively, R a Is that
6. The polyurethane elastomer of claim 5, wherein R a Is- (CH) 2 ) 6 -。
7. The polyurethane elastomer of claim 1, wherein the polyether glycol or polyester glycol is selected from the group consisting of polytetrahydrofuran glycol, polyethylene adipate glycol, polyethylene glycol adipate, 1, 4-butanediol polyadipate glycol, and polyethylene glycol;
and/or R c Is a bond or- (CH) 2 ) 4 -。
8. The polyurethane elastomer of claim 1,
the structural formula of the polyurethane elastomer is shown as formula I-1:
wherein m is 38 and n is 28; the polyurethane elastomer has a molecular weight distribution index (PDI) of 1.66;
alternatively, the structural formula of the polyurethane elastomer is shown as formula I-2:
wherein m is 35, n is 28; the polyurethane elastomer has a molecular weight distribution index (PDI) of 1.86;
alternatively, the structural formula of the polyurethane elastomer is shown as formula I-3:
wherein m is 28 and n is 28; the polyurethane elastomer has a molecular weight distribution index (PDI) of 2.23;
alternatively, the structural formula of the polyurethane elastomer is shown as formula I-4:
wherein m is 22 and n is 28; the polyurethane elastomer has a molecular weight distribution index (PDI) of 1.96.
9. A process for the preparation of a polyurethane elastomer as claimed in any one of claims 1 to 8, characterized in that it comprises the following steps:
(1) In a solvent, under the protection of gas, under the temperature of 60-80 ℃, under the action of a catalyst, carrying out a prepolymerization reaction on the compound A and the compound B to obtain a prepolymer;
(2) In a solvent, under the protection of gas, carrying out polymerization reaction on the prepolymer obtained in the step (1) and a compound C at the temperature of 30-50 ℃ to obtain a polyurethane elastomer shown in a formula I;
wherein R is a 、R b And R is c And m is as defined in any one of claims 1 to 7; by a means ofThe mol ratio of the compound A to the compound B to the compound C is 2 (0.9-1.1) to 0.9-1.1.
10. The method for producing a polyurethane elastomer according to claim 9, wherein the molar ratio of the compound a, the compound B and the compound C is 2:2:1.
11. A process for preparing a polyurethane elastomer as claimed in claim 9, wherein,
the compound A isThe compound B is->n=28, said compound C is +.>
Or, the compound A isThe compound B isn=28, said compound C is +.>
Or, the compound A isThe compound B is->n=28, said compound C is +.>
Or, the compound A isThe compound B is->n=28, said compound C is +.>
12. A process for preparing a polyurethane elastomer as claimed in claim 9, wherein,
in the step (1) or the step (2), the solvent is a polar organic solvent;
and/or in the step (1) or the step (2), the gas is nitrogen;
and/or in the step (1), the catalyst is an organotin catalyst or a tertiary amine catalyst;
and/or, in the step (1), the time of the prepolymerization reaction is 2-5 h;
and/or, in the step (1), the temperature of the prepolymerization reaction is 70 ℃;
and/or, prior to step (1), subjecting said compound B to a water removal treatment;
and/or, in the step (2), the temperature of the polymerization reaction is 40 ℃;
and/or, in the step (2), the time of the polymerization reaction is 10-20 h;
and/or, the step (2) is as follows: after the prepolymerization reaction in the step (1) is finished, cooling the temperature of the system to 30-50 ℃, and directly adding a solution of a compound C into the system to perform polymerization reaction;
and/or, after the polymerization reaction in the step (2) is finished, carrying out post-treatment.
13. A process for preparing a polyurethane elastomer as claimed in claim 12, wherein,
in the step (1) or the step (2), the solvent is one or more of N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide;
and/or in step (1), the catalyst is dibutyltin dilaurate, stannous octoate, triethylenediamine, bis (dimethylaminoethyl) ether, or N, N-dimethylcyclohexylamine;
and/or the mass ratio of the catalyst to the compound A is 1: (100-500);
and/or, in the step (1), the time of the prepolymerization reaction is 3h;
and/or, the water removal treatment is to stir the compound B at 110 ℃ under vacuum for 1h;
and/or, in the step (2), the time of the polymerization reaction is 15h;
and/or, the post-treatment is to heat and volatilize the solvent from the reaction liquid after the polymerization reaction is finished, and then vacuum drying is carried out.
14. A process for preparing a polyurethane elastomer as claimed in claim 13, wherein,
in the step (1) or the step (2), the solvent is N, N-dimethylacetamide;
and/or, the temperature of the heating is 80 ℃;
and/or, the heating time is 12h;
and/or, the drying temperature is 80 ℃;
and/or, the drying time is 24 hours.
15. Polyurethane elastomer, characterized in that it is produced by the production process according to any one of claims 9 to 14.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911396675.1A CN113121782B (en) | 2019-12-30 | 2019-12-30 | Polyurethane elastomer raw material, polyurethane elastomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911396675.1A CN113121782B (en) | 2019-12-30 | 2019-12-30 | Polyurethane elastomer raw material, polyurethane elastomer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113121782A CN113121782A (en) | 2021-07-16 |
| CN113121782B true CN113121782B (en) | 2024-01-26 |
Family
ID=76767957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911396675.1A Active CN113121782B (en) | 2019-12-30 | 2019-12-30 | Polyurethane elastomer raw material, polyurethane elastomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113121782B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115838464A (en) * | 2021-09-18 | 2023-03-24 | 四川大学 | Preparation method of waterborne room temperature self-repairing polyurethane containing twisted multiple hydrogen bonds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1248181A (en) * | 1969-01-22 | 1971-09-29 | Bayer Ag | Segmented polyurethane elastomers |
| US4286014A (en) * | 1978-01-31 | 1981-08-25 | Toray Industries, Incorporated | Composite sheet material |
| CN109265636A (en) * | 2018-08-10 | 2019-01-25 | 四川大学 | Novel high-performance THERMALLY REVERSIBLE COVALENT polymer based on amide groups urea bond and preparation method thereof |
-
2019
- 2019-12-30 CN CN201911396675.1A patent/CN113121782B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1248181A (en) * | 1969-01-22 | 1971-09-29 | Bayer Ag | Segmented polyurethane elastomers |
| US4286014A (en) * | 1978-01-31 | 1981-08-25 | Toray Industries, Incorporated | Composite sheet material |
| CN109265636A (en) * | 2018-08-10 | 2019-01-25 | 四川大学 | Novel high-performance THERMALLY REVERSIBLE COVALENT polymer based on amide groups urea bond and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113121782A (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110591542A (en) | Disulfide bond and hydrogen bond containing dual self-repairing polyurethane coating for invisible car cover and preparation method thereof | |
| US11053345B2 (en) | Polyurethane polymer, method for preparing the same and use thereof | |
| US20200308407A1 (en) | Transparent rollable folded polysiloxane film and preparation and self-repairing method thereof | |
| CN109776804B (en) | Cross-linkable POSS reinforced polyurethane nano hybrid material and preparation method thereof | |
| CN106543437A (en) | A kind of cross-linking type low thermal expansion coefficient polyimide thin film and preparation method thereof | |
| CN109111562B (en) | Self-repairing polyurethane, preparation method thereof and self-repairing method thereof | |
| CN113121782B (en) | Polyurethane elastomer raw material, polyurethane elastomer and preparation method thereof | |
| CN115353609B (en) | Repairable and reinforced high-performance polyurethane elastomer and preparation method thereof | |
| CN108484868B (en) | Self-healing material based on polyurethane and preparation method thereof | |
| CN115232465A (en) | Preparation method of tough self-repairing material capable of realizing self-repairing in seawater | |
| CN113004484A (en) | Low-temperature-resistant oil-resistant thermoplastic silicone rubber-polyurethane elastomer and preparation method thereof | |
| CN109575233B (en) | Polysiloxane polyether type polyurethane elastomer with high mechanical property and preparation method thereof | |
| CN109134817B (en) | Self-repairing polyurethane elastomer responding to ultraviolet light stimulation and preparation method thereof | |
| CN110872370A (en) | Application of low-phosphorus cross-linking agent in preparation of polyurethane film | |
| CN113061229B (en) | Weather-resistant heat-resistant high-toughness room-temperature self-repairing polyurethane urea elastomer | |
| CN110845699B (en) | Colorless high-transparency high-tensile tear-resistant room-temperature self-repairing polyurea elastomer and preparation method thereof | |
| US20210317273A1 (en) | Method for preparing topological elastomers with highly branched structures, low modulus and high elasticity | |
| CN110041502B (en) | Thermoplastic polyurethane elastomer and preparation method and application thereof | |
| CN114773557B (en) | Corrosion-resistant and weather-resistant polyurethane elastomer for surface protection application | |
| CN113278128B (en) | Waterborne polyurethane/polyurea with fluorine-containing side chain and preparation method thereof | |
| US11202986B2 (en) | Plasticization-resistant polyurethane membrane and preparation method thereof | |
| CN114133519B (en) | Thermoplastic polyurethane elastomer and preparation method and application thereof | |
| CN108084391A (en) | A kind of polyurethane and preparation method thereof | |
| CN117624538A (en) | Ultra-high-performance transparent self-repairing polyurethane-urea film capable of being recycled and preparation method thereof | |
| CN116622046B (en) | Post-crosslinkable high molecular weight polyurethane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |